盐酸头孢他美酯分散片有关物质的色谱-质谱结构鉴定

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目的:采用液相色谱-飞行时间质谱法对盐酸头孢他美酯分散片中有关物质进行结构鉴定。方法:采用HPLC梯度洗脱方法对有关物质进行测定,色谱柱为C_(18)(4.6 mm×250 mm,5μm),流动相A为0.005 mol·L~(-1)四丁基氢氧化铵溶液(用磷酸调节p H至4.5),流动相B为乙腈,梯度洗脱,流速1.0mL·min~(-1),检测波长为232 nm;采用液相色谱-飞行时间质谱技术对未知杂质进行鉴定,色谱柱为C_(18)(2.1 mm×100 mm,2.7μm),流动相A为10 mmol·L~(-1)醋酸铵溶液,流动相B为甲醇-乙腈(50∶50),梯度洗脱,流速0.2mL·min~(-1),采用正离子扫描(ESI+)方式,在m/z 100~1 200范围内进行质谱扫描。结果:头孢他美酯与其有关物质能较好地分离,检测出10个有关物质,Ⅰ:(6R,7R)-3-苯乙烯基-7-[(Z)-2-(2-特戊酰氨基-4-噻唑基)-2-(甲氧亚氨基)乙酰氨基]-8-氧代-5-硫杂~(-1)-氮杂双环[4,2,0]辛-2-稀-2-甲酸新戊酰氧甲酯;Ⅱ:(6R,7R)-3-甲基-7-[(Z)-2-(2-氨基-4-噻唑基)-2-(甲氧亚氨基)乙酰氨基]-8-氧代-5-硫杂~(-1)-氮杂双环[4,2,0]辛-2-稀-2-羧酸;Ⅲ:(6R,7R)-3-甲基-7-[(Z)-2-(2-特戊酰氨基-4-噻唑基)-2-(甲氧亚氨基)乙酰氨基]-8-氧代-5-硫杂~(-1)-氮杂双环[4,2,0]辛-2-稀-2-羧酸;Ⅳ:(6R,7R)-3-甲基-7-[(Z)-2-(2-羟甲基氨基-4-噻唑基)-2-(甲氧亚氨基)乙酰氨基]-8-氧代-5-硫杂~(-1)-氮杂双环[4,2,0]辛-2-稀-2-甲酸新戊酰氧甲酯;Ⅴ:(6R,7S)-3-甲基-7-[(Z)-2-(2-氨基-4-噻唑基)-2-(甲氧亚氨基)乙酰氨基]-8-氧代-5-硫杂~(-1)-氮杂双环[4,2,0]辛-2-稀-2-甲酸新戊酰氧甲酯;Ⅵ:(6R,7R)-3-甲基-7-[(Z)-2-[2-(2-甲氨基-4-噻唑基)-2-(甲氧亚氨基)乙酰氨基]-2-(甲氧亚氨基)乙酰氨基]-8-氧代-5-硫杂~(-1)-氮杂双环[4,2,0]辛-2-稀-2-甲酸新戊酰氧甲酯;Ⅶ:(6R,7R)-3-甲基-7-[(Z)-2-[2-(2-氨基-4-噻唑基)-2-(甲氧亚氨基)乙酰氨基]-2-(甲氧亚氨基)乙酰氨基]-8-氧代-5-硫杂~(-1)-氮杂双环[4,2,0]辛-2-稀-2-甲酸新戊酰氧甲酯;Ⅷ:(6R,7R)-3-甲基-7-[(Z)-2-(2-特戊酰氨基-4-噻唑基)-2-(甲氧亚氨基)乙酰氨基]-8-氧代-5-硫杂~(-1)-氮杂双环[4,2,0]辛-2-稀-2-甲酸新戊酰氧甲酯;Ⅸ、Ⅹ:((6S,7S)-3-甲基-7-((Z)-2-(甲氧基亚氨基)-2-(2-((((4-((Z)~(-1)-(甲氧基亚氨基)-2–(6R,7R)-3-甲基-8-氧代-2-(((新戊酰氧基)甲氧基)羰基)-5-硫杂~(-1)-氮杂双环[4.2.0]辛-2-烯-7-基)氨基)-2-氧代乙基)-2-噻唑基)氨基)甲基)氨基)-4-噻唑基)乙酰氨基)-8-氧代-5-硫杂~(-1)-氮杂双环[4.2.0]辛-2-烯-2-羧酸,它们都具有头孢菌素的基本母核7-氨基去乙酰氧基头孢烷酸(7-ADCA),其中有关物质Ⅰ、Ⅲ、Ⅵ尚未见文献报道。结论:色谱-质谱联用技术能有效地鉴定盐酸头孢他美酯分散片中有关物质,为其生产工艺和质量控制提供参考依据。 OBJECTIVE: To identify the related substances in Ceftazidime Hydrochloride Dispersible Tablets by liquid chromatography-time of flight mass spectrometry. Methods: The related substances were determined by HPLC gradient elution. The chromatographic column was C 18 (4.6 mm × 250 mm, 5 μm), and the mobile phase A was 0.005 mol·L -1 tetrabutylammonium hydroxide solution Adjusted pH to 4.5 with phosphoric acid), mobile phase B was acetonitrile, gradient elution at a flow rate of 1.0 mL · min -1 with a detection wavelength at 232 nm. Unidentified impurities were identified by liquid chromatography-time of flight mass spectrometry , The column was C 18 (2.1 mm × 100 mm, 2.7 μm), the mobile phase A was 10 mmol·L -1 ammonium acetate solution, the mobile phase B was methanol-acetonitrile (50:50), the gradient The elution was carried out at a flow rate of 0.2 mL · min ~ (-1) and the mass spectrometry was performed in the range of m / z 100 ~ 1 200 using positive ion scanning (ESI +). RESULTS: Ceftazidime and its related substances were well separated and 10 related substances were detected. Ⅰ: (6R, 7R) -3-styryl-7- [(Z) -2- Thiazolyl) -2- (methoxyimino) acetamido] -8-oxo-5-thia- (1) -azabicyclo [4,2,0] oct-2- 2-methoxyphenylacetic acid methyl ester; 2-Methoxy-2-methoxyphenylacetyl ester; (6R, 7R) -3-oxo-5-thia- -3-methyl-7- [(Z) -2- (2- pivaloylamino-4-thiazolyl) -2- (methoxyimino) acetamido] -8-oxo- Azabicyclo [4,2,0] oct-2-one 2-carboxylic acid; IV: (6R, 7R) -3- methyl-7- [(Z) -2- 2-hydroxymethylamino-4-thiazolyl) -2- (methoxyimino) acetamido] -8-oxo- Octadecanoic acid pivaloyloxymethyl ester; V: (6R, 7S) -3-methyl-7- [(Z) -2- - (methoxyimino) acetamido] -8-oxo-5-thia- (1) -azabicyclo [4,2,0] oct-2- Ester; VI: (6R, 7R) -3-Methyl-7 - [(Z) -2- [2- - 2- (methoxyimino) acetylamino] -8-oxo-5-thia- (1) -azabicyclo [4,2,0] oct-2-dilute-2-carboxylic acid pivaloyloxy Methyl ester; VII: (6R, 7R) -3-Methyl-7 - [(Z) -2- [2- -2- (methoxyimino) acetamido] -8-oxo-5-thia- (1) -azabicyclo [4,2,0] oct-2- Oxymethyl ester; VIII: (6R, 7R) -3-methyl-7 - [(Z) -2- (2- pivaloylamino-4- thiazolyl) -2- (methoxyimino) acetamido ] -8-oxo-5-thia- (1) -azabicyclo [4,2,0] oct-2- , 7S) -3-methyl-7- ((Z) -2- (methoxyimino) -2- ((Pivaloyloxy) methoxy) carbonyl) -5-thia-1- (6R, 7R) -3- methyl- 2-en-7-yl) amino) -2- oxoethyl) -2- thiazolyl) amino) methyl) amino) -4-thiazolyl) acetamido ) -8-oxo-5-thia- (1) -azabicyclo [4.2.0] oct-2-ene-2-carboxylic acid, all of which have the basic parent nucleus of cephalosporins Acetoxycephalosporanic acid (7-ADCA), of which related substances Ⅰ, Ⅲ, Ⅵ have not been reported in the literature. Conclusion: Chromatography-mass spectrometry can effectively identify the related substances in Ceftazidime Hydrochloride dispersible tablets and provide a reference for its production process and quality control.
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